Novel Approaches to Immobilized Heteropoly Acid (HPA) Systems for High Temperature,

Low Relative Humidity Polymer-Type Membranes

Andrew M. Herring Colorado School of Mines

Mathew H Frey 3M Corporate Research Materials Laboratory

5/18/12 Project ID FC039

This presentation does not contain any proprietary, confidential, or otherwise restricted information

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Overview

• Project Start: April 1st 2006 • Project end: September 30th 2011 (6

month NCE) • 100% Complete

– C Performance – B Cost – A Durability

• Total project funding – DOE - $1,500K – Cost Share - $376K – FY11 Funding - $100K – Planned FY12 Funding - $0

Timeline

Budget

Barriers

• 3M - Industrial • Project lead - CSM

Partners

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Objectives/Relevance •Overall •Demonstrated a hybrid HPA polymer (polyPOM) from

HPA functionalized monomers with: – σ >0.1 S cm-1 at 120°C and <50% RH (Barrier C)

• 2010 •Optimize hybrid polymers in practical systems for proton conductivity and mechanical properties - achieved (Barrier C and A)

• 2011 •Optimize hybrid polymers for proton conductivity, mechanical properties, and oxidative stability/durability (Barrier A, B, and C)

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Unique Approach • Materials Synthesis

based on HPA Monomers and attachment to commercially viable polymers, Novel “High and Dry” proton conduction pathways mediated by organized HPA moieties – A NEW Ionomer System

• Generation I films – Acrylate co-monomers, polymer system in a kit,

• Generation II films – TFVE co-monomers

• Generation III films – Attachment to 3M DyneonTM Fluoroelastomers

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Approach - use Functional Inorganic Super Acids: Heteropoly acids

• + – High proton conduction, e.g. 0.2 S cm-1 at RT for 12-HPW – Thermally stable at the temperatures of interest, <200 °C – Synthetically Versatile - even simple salts are interesting

• +/- – Water soluble – but easily immobilized by

functionalization in polymers – Reduced form – electrically conductive, but fuel cell

membrane environment generally oxidizing, however can be used to advantage on anode

– Proton conductivity dependency on water content/interaction with polar/protonic components

– Known to decompose peroxides

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Previous Accomplishments Generation I Films – PolyPOM85v/BA

Films Generally thick but ASR <0.02 Ω cm2

Progress - Generation II Films TFVE-HPA copolymers

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• Trifluorovinyl ethers (TFVE) functionalized HPA monomers synthesized on <100g scale

• Trifluorovinyl ethers polymerize thermally

• Large number of co-monomers available

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0.0001

0.0010

0.0100

0.1000

40 50 60 70 80 90 100 110 120

Con

duct

ivity

(S/c

m)

Temperature (oC)

Conductivity vs. Temperature for MCK-VII-83A at 50% RH 3M Control 825 MCK-VII-83A, Sample 1MCK-VII-83A, Sample 2 MCK-VII-26A - EA=6.7 kJ/molMCK-VII-35A - EA=No Data MCK-VII-35B - EA=No DataMCK-VII-89A1 (Ea=20.79 kJ/mol) MCK-VII-89A-2 (Ea=18.41 kJ/mol)MCK-VII-90A (Ea=15.96 kJ/mol) MCK-VII-96A - EA=14.9 kJ/molMCK-VII-97A - EA=15.9 kJ/mol MCK-VII-100A

Proton Conductivity - Variable

• Appears to synergistically vary based on film forming, chemistry, and morphology – complex design space

0.000

0.010

0.020

0.030

0.040

0.050

0.060

0.070

0.080

0.090

0.100

0 1 2 3 4Membrane Composition

Con

duct

ivity

(S/c

m)

1) 75% HSiW11O39[(TFVE-Si)2O] / PVdF-HFP2) 67% HSiW11O39[(TFVE-Si)2O] / PVdF-HFP / Comp. IV 3) 66% HSiW11O39[(TFVE-Si)2O] / PVdF-HFP / TFVE-biphenyl4) 66% HSiW11O39[(TFVE-Si)2O] / PVdF-HFP / Comp. VII

For hybrid TFVE membranes

Wt% based on HSiW11O39[(TFVE-Si)2O] monomer present

Conductivity Dependence on Morphology at 80 °C, RH 80%

• 1st Approximation co-monomer chemistry important 9

95% RH Script Conductivity Results

State of the art film same ASR as 3M 825EW but 7 x as thick

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SAXS, 25%, 50%, 75% and 95% RH and 80 oC DVS, 60 oC

Crystalline Phases observed at low RH

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• Bragg peaks observed at low RH in SAXS, Phase changes observed at low RH in DVS

• Amorphous phase is the highly conducting phase • Water content decreases on RH cycling

(implies hard to measure equilibrium properties and increasing brittleness on cycling)

1.5

38 1

.418

1.2

51

8 7 6 5 4 3 2 1 PPM

1.6 1.5 1.4 1.3

1H NMR spectrum for 4-[(Trifluorovinyl)oxy]bromobenzene

7.6

84

7.1

19

3.8

70

1.2

41

1.0

4

1.0

0

3.4

1

5.2

4

10 8 6 4 2 0 PPM

1H NMR spectrum for pure 4-[(Trifluorovinyl)oxy]phenyltriethoxysilane

Digital vapor sorption – total over 2 relative humidity cycles, based on initial mass (Mo) •HPA containing membranes have considerably less water uptake than PFSAs 15

Mass % Water Uptake of Three Different Membranes

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n

*n

CF3F F

FF

OH

Br

ONa

Br

OCH3 CF2 C C CH

CF3

CF CF2 CF

CF3

Br

phosphonation

OCH2 CF2 C C CH

CF3

CF CF2 CF

CF3

PO(OEt)2

hydrolysis OCH2 CF2 C C CH

CF3

CF CF2 CF

CF3

PO(OH)2

HPA attachment

OP

OCH2 CF2 C C CH

CF3

CF CF2 CF

CF3

P

OCH2 CF2 C C CH

CF3

CF CF2 CF

CF3

O

dehydrofluorination

HPA 20-40wt%

Concentration: mole% of Br: 5-20%

of monomer units

Yield: 47%

Yield: 90%

Yield: 50%

Progress, Generation III Polymer – Synthesis

K8[SiW11O39]•13H2O

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HPA attached, acidified hybrid fluoropolymer (crumb) was dissolved in DMSO at 4% concentration. Solution was then cast on ClearSIL®T10

silicone coated liner (or Kapton® polyimide (PI) liner in some cases). The resulting membrane below was first heated at 120ºC for 10min; Temp

was then increased to 180ºC, membrane was heated at 180ºC for 10min.

HPA attached hybrid fluoropolymer membrane cast on T10. • Film processing critical to high performance

Membrane Processing

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AFM imaging --- Phase Image (recorded at CSM)

10um 2um

Morphology

Proton Conductivity, 80°C

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Conductivity vs Relative Humidity for3M Generation III polymer (HPA-PVDF-HFP)

0.0001

0.0010

0.0100

0.1000

1.0000

10 20 30 40 50 60 70 80 90 100

Relative Humidity (%RH)

Con

duct

ivity

(S/c

m)

3M Ionomer Control - 825EW PFSAHP8/30min dissolution - 180C/5min anneal - PI liner (4248-34B)HP9+/2hr dissolution - 180C/8min anneal - PI liner (4248-32A)HP9+/2hr dissolution - 180C/8min anneal - T10 liner (4248-32B)HP9+/2hr dissolution - 170C/5min anneal - PI liner (4248-33A)HP9+/2hr dissolution - 170C/5min anneal - T10 liner (4248-33B)

80ºC Measured by Michael

Emery, 3M TestEquity oven,

atmospheric pressure Bekktech sample fixture

HP: Hot plate setting PI: Kapton® polyimide

T10: ClearSIL®T10 silicone coated

*** Incompletely

dissolved in DMSO (casting solvent); tested in November 2010; 37% HPA

***

• Film forming critical to high performance

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Tensile Testing

0

5

10

15

20

25

30

35

0 100 200 300

Strain (%)

Stre

ss (M

Pa)

3M 800EW PFSA3M 2009 80-HPA-vinyl-acrylate Hybrid3M 2010 HPA-[PVDF-co-HFP]

• Functionalized Polymer gives stronger film could be tailored by Dyneon chemistry

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Manufacturing Feasibility Assessment Selected high-level comments: • “This is a complex fine chemical synthesis.”… “Fine chemical processing is a lot like this.” • “Chemically, there are no showstoppers.”…“No chemistry here that scares me.” • “I wouldn‘t be too discouraged.” • “There are no exotic conditions…normal glassware.” Selected detailed comments: • “Process optimization is needed to improve volume utilization.” • “% solids of each of these process steps will have a big impact on your reactor volume efficiency.” • “A lot of dissolving and drying” … “Can you avoid drying to a solid every time?”…“Can you do any

steps neat?” • “Can you do solvent exchanges?”…”keep it soluble?” • “Can you use a different PVDF-HFP?…some may be easier than others…different molecular weight?” • “To use less solvent, could you carry some impurities along, and then clean up just once, at the end?” If one were to pursue this material commercially at 3M, next steps: • Initiate “New Materials Introduction” program within MRD. • Review for entry into MRD lab. • Carry out focused work against detailed comments above.

Overall Conclusions: • The HPA-modified PVDF-HFP preparation appears likely to be feasible in manufacturing. • Any additional development work on this type of material should include objectives related

to solvent usage and process simplicity, as suggested above.

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Collaborations

• Prime: Colorado School of Mines – STEM University • Sub: 3M Corporate Material Research Laboratory • Other Collaborators: the following have agreed to test

membranes ex-situ or as MEAs from promising films. – 3M Fuel Cell Components Group – ProtonOnsite – GM (has offered to test promising materials) – Nissan Technical Center, North America (has offered to test

promising materials)

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• New series of films with pure TFVE monomer, structured diblocks • Improve Dyneon attachment chemistry with polymer designed for

HPA attachment • Incorporate work on Zr phosphonate hybrid films.

Proposed Future Work (unfunded)

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• Consistently High Proton Conductivity in Robust films • 2 New Film Chemistries optimized

– High Oxidative stability – Excellent Mechanical properties

Summary

DOE target 2017/ Ω cm2

CSM TFVE-HPA 2011/ Ω cm2

Thickness /µm

CSM TFVE-HPA if 10 µm

120/40% RH 0.02 0.43 50%RH

180 0.02

80/85% RH 0.02 0.13 130 0.01 30/90%RH 0.03 0.026

95%RH 150 0.002

The data presented is for the best performing film at each condition. Further work is required to fully optimize one

material for all conditions